Compositions and methods for the stabilization of clay containing soils

ABSTRACT

Polysaccharides may be partially oxidized by oxidative opening of a monosaccharide unit while still retaining glycosidic bonds. Such polysaccharides may be further functionalized with an amine moiety at a site of oxidative opening. Polysaccharides that are partially oxidized and amine-functionalized in this manner may be combined with an aqueous liquid to form compositions suitable for stabilizing clays in clay-containing formations. Clay stabilization may promote reduced swelling of the clays in the presence of water.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 15/001,479, filed on Jan. 20, 2016, which claims the benefit ofpriority under 35 U.S.C. § 119 of U.S. Provisional Patent Application62/142,886, filed on Apr. 3, 2015, each of which is incorporated hereinby reference in its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND

The present invention is directed to the production of polysaccharidesand polysaccharide derivatives and, in particular, compositions, tools,systems and methods for the stabilization of clays, shales and otherclay-containing materials and soils with polymers containing dextran,dextran derivatives, and other substituted polysaccharides.

Clay poses challenges, as it is well known for swelling in the presenceof water. Within its crystalline layers, clay contains cations,typically sodium, which occupy base-exchange sites. Upon contact withwater, these cations are solubilized resulting in clay instability andoften swelling with complete breakdown of the solid into liquid slurry.When clay swells with the absorption of water, there is surface swellingand/or osmotic swelling due to absorption.

The ability of the clay-containing land to permit drilling, passage ofliquids, or fracturing fluids as well as hydrocarbons, is diminished,impeding production. A number of clay stabilizers are available such aspotassium chloride which functions in an ion exchange process. Potassiumchloride reduces clay swelling by replacing a native clay cation with apotassium ion and/or creating an overall negative charge on individualclay layers. This charge is compensated for by cations located in theinterlayer region, which can be freely exchanged. Accordingly, potassiumsaturated clays have a reduced tendency to swell and absorb liquids,thus increasing the excavation process and reducing excavation costs.

The cation exchange capacity of the mineral depends on crystal size, pH,and the particular type of cation involved. These may not only be smallions, but also poly-cations. Also, the potassium ion is over seventypercent larger than the sodium ion. Although potassium ions areeffective at preventing swelling, high levels are required whichcontaminates the area. In addition, potassium chloride is hazardous andincompatible with other materials used, for example, in drilling andmining operations. Potassium negatively impacts fracturing fluids suchguar, xanthan, welan, scleroglucan and polyacrylamide polymers, each ofwhich is utilized in one or another excavation process.

Accordingly, there is a need in the art for a safe and effective claystabilizer which is effective in all or substantially all of the clayconstituents in a heterogeneous clay/shale formation.

SUMMARY

The present invention overcomes the problems and disadvantagesassociated with current strategies and designs and provides new tools,compositions and methods for stabilizing soils and other materials.

One embodiment of the invention is directed to soil stabilizationprocesses comprising: providing a composition comprised of a polymerfunctionalized to contain one or more amine and/or alkyl moieties;mixing the composition with an aqueous liquid, such as for example,water or wellbore fluid, to form a stabilization solution; and applyingthe stabilization solution to a soil. Preferably the soil stabilizationprocess is performed in association with a mining operation, anexcavation operation, or a drilling operation and performed at greaterthan ambient, ambient or less than ambient temperatures, and thecomposition may be mixed with the soil. Preferably soil comprises one ormore of minerals, dirt, organic material, inorganic material, shale, redmud, rock, mudrock, clay, slag, and tailings. Preferably the compositionis a liquid at a pH of from about 5-8 and a viscosity of about 100-500cP. Also preferably the functionalized polymer comprises a saccharide, apolysaccharide or a derivative thereof, such as, for example, dextran,guar gum, scleroglucan, welan, xanthan gum, chitosan, schizophyllan,levan, cellulose or a combination thereof. Wherein the polymer is adextran, preferably the dextran has a molecular weight of about 3 kD toabout 2,000 kD coupled to from 0-3 alkylamine moieties permonosaccharide unit and 20 percent or more of the monosaccharide unitscontain amine, alkyl and/or alkylamine moieties. Also preferably thepolymer contains one or more amine moieties such as, for example, one ormore amine, diamine and/or tetra-amine moieties, or one or more alkylmoieties such as, for example, aldehyde, alkane, alkene, alkyne, aryl orother hydrocarbon, or one or more alkyl/amine moieties. Preferably thecomposition contains no detectable sodium and also that the compositionis not harmful to the environment. Preferably the composition furthercontains a surfactant, a defoaming agent, a detergent, a chelator, abuffer, an identifiable tag or a combination thereof. The process mayfurther comprise monitoring the identifiable tag in the environment suchas, for example, by tracking disbursement of the identifiable tag,tracking patterns of disbursement of the identifiable tag, trackingtiming of degradation of the identifiable tag, and/or combinationsthereof.

Another embodiment of the invention is directed to a soil stabilizationprocess comprising: providing a composition containing a functionalizedpolysaccharide wherein multiple saccharide units of the functionalizedpolysaccharide are coupled to amine and/or alkyl moieties; forming astabilization solution containing the composition; and applying thestabilization solution to a soil. Preferably the soil stabilizationprocess is performed in association with a mining, an excavation, or adrilling operation and the stabilization solution prevents soil swellingwhen the soil comes into contact with an aqueous composition. Preferablythe stabilization solution is flushed into a drilled space before,during or after drilling or other excavation. Also preferably thepolysaccharide is dextran containing multiple alkyl, amine and/oralkyl/amine moieties wherein, for example, the alkyl moieties areselected from the group consisting of aldehyde, alkane, alkene, alkyne,aryl moieties, and combinations thereof, the amine moieties are selectedfrom the group consisting of amine, diamine, tetra-amine moieties, andcombinations thereof, or the alkylamine moieties are selected from thegroup consisting of combinations of hydrocarbon/amine moieties.Preferably the stabilization solution is not harmful to the environmentand safe for handling without any requirements for specialized disposal(e.g., no risks as compared with hazardous disposal), and may furthercomprise mixing the composition with an aqueous liquid to form thestabilization solution. Preferably the polysaccharide comprises dextran,guar gum, scleroglucan, welan, xanthan gum, chitosan, schizophyllan,levan or cellulose, and contains multiple saccharide units wherein amineand/or alkyl moieties are coupled to at least 20 percent of thesaccharide units, preferably 50 percent or more of the saccharide units.Preferably the composition further comprises a solvent such as, forexample, a water-based or a polar solvent. Also preferably thestabilization solution further comprises an additive such as, forexample, a surfactant, a defoaming agent, a detergent, a chelator, abuffer, an identification tag or a combination thereof. Preferably thestabilization solution further contains a drilling fluid and thedrilling fluid is xanthan gum.

Another embodiment of the invention is directed a composition comprisinga functionalized polymer, preferably of a polysaccharide, containingprimary amine and/or alkyl group substitutions or moieties along therepeating units of the polymer chain. Preferably the polymer comprisesone or more of dextran, guar gum, scleroglucan, welan, xanthan gum,chitosan, schizophyllan, levan, cellulose or combinations thereof. Alsopreferably, the polymer contains substitutions along 1-100 percent ofits repeating units, the wherein the primary amine substitutions arepreferably monoamines, diamines, tri-amines, tetra-amines moieties orcombinations thereof, the alkyl group substitutions are methyl, ethyl,propyl, isopropyl, alkane, alkene, alkyne, aryl or hydrocarbon moieties,or combinations thereof, and alkyl moiety substitution comprise from 1to 3 carbons. Preferably the composition further comprises a solventsuch as, for example, a water-based or polar solvent. Also preferably,the composition further comprises an additive such as, for example, asurfactant, a defoaming agent, a detergent, a chelator, a buffer or acombination thereof. Also preferably, the composition of the inventionis a stabilizing composition which is mixed with a fluid, for examplebut not limited to water, a drilling fluid, and an excavation fluid, andused to stabilize a soil being excavated for drilling or miningoperations. Stabilization includes reduction and/or prevention of soilswelling. Preferred drilling fluids include, but are not limited toxanthan gums.

Another embodiment of the invention comprises methods of stabilizingsoil comprising contacting the soil with the stabilizing compositions ofthe invention containing one or more functionalized polymers of theinvention. Preferably the stabilizing composition comprises afunctionalized polymer of the invention that is flushed into a spaceexcavated before, during or after excavation, such as drilling orfracking. Preferably the composition prevents soil swelling when thesoil comes into contact with a composition comprising water. Alsopreferably, the stabilizing composition is mixed with a drilling fluid.

Another embodiment of the invention comprises methods of stabilizingsoil comprising contacting compositions of the invention at a work sitesuch as, for example, a well, a mine or an excavation site. Preferablycontacting comprises mixing a material and the functionalized polymer ofthe invention to form a thixotropic mixture, and depositing thethixotropic mixture at a work site. Preferred materials comprise soilssuch as clays, shales and the like.

Another embodiment of the invention comprises methods of stabilizing redmud which comprises contacting the red mud with the stabilizingcomposition of the invention containing one or more functionalizedpolymers. Preferably the red mud is a by-product of a mining process.

Other embodiments and advantages of the invention are set forth in partin the description, which follows, and in part, may be obvious from thisdescription, or may be learned from the practice of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A Structural depiction of amino dextran (partially oxidized sugardextran diethyl amine).

FIG. 1B Structural depiction of ethylamine dextran.

FIG. 1C Structural depiction of diethylethanolamine dextran.

FIG. 1D Structural depiction of amino levan (partially oxidized sugarlevan diethyl amine).

FIG. 1E Structural depiction of ethylamine levan.

FIG. 1F Structural depiction of diethylethanolamine levan.

FIG. 1G Structural depiction of amino guar (partially oxidized sugarguar diethyl amine).

FIG. 1H Structural depiction of ethylamine guar.

FIG. 1I Structural depiction of diethylethanolamine guar.

DETAILED DESCRIPTION

Drilling, mining and other excavating often requires the use ofhazardous and high risk chemicals. For example, it is often necessary tostabilize a ground area in preparation for drilling or mining.Stabilization typically involves treating the soil with large amount ofpotassium chloride. The potassium ions displace native cations of theclay in the soil preventing swelling which would otherwise damage thedrilling equipment. The concentrations of potassium chloride that arenecessary to prevent swelling destroy plant life in the treated areasand eventually concentrate in run off and/or contaminate the aquifer. Inaddition, potassium chloride is useless in extremely cold climatesbecause the potassium crystallizes out of solution becoming locked intocrystals. These crystals do not allow for the displacement of othercations and, thus the addition of potassium chloride is unable toprevent soil swelling.

It was surprisingly discovered that polymers and, preferablyfunctionalized forms of polysaccharides could be used to prevent soilswelling, especially the swelling of soils that are high in claycontent, and also in red mud stabilization and disposal procedures.Functionalized polymers of the invention are useful to stabilize red mudcreated as a consequence of the Bayer process, which is used, forexample, in the production of aluminum.

Polymers such as dextran and other polysaccharides are highlywater-soluble molecules with structures that do not change underextremes of temperature and pH. Unlike potassium chloride, there aretypically no or minimal issues associated with crystallization of thepolymer when used at the low temperatures that exist when working incold climates. Polymers such as polysaccharides and functionalizedpolysaccharides and derivatives thereof of the invention areenvironmentally safe, nonhazardous to work with and generallybiocompatible. Dextran and other polysaccharide molecules are alsobiodegradable and pose little to no negative impact to plants, animalsand other organisms or populations, or on the environment in general,even when used in high concentrations. Polysaccharides andpolysaccharide derivatives of the invention that are useful asfunctionalized polymers of the invention simply and rapidly degrade inthe environment into harmless components. Also, functionalizedpolysaccharide and functional polysaccharide derivatives (e.g.,functionalized polymers containing conservative modifications, deletionsand/or substitutions that remain functional) of the invention arepreferably used as non-toxic, low viscosity liquids. As such, they areeasily transportable, requiring no special handling as would hazardousmaterials, and thus readily available directly at the site of use. Thisready-to-use availability eliminates time otherwise required forpre-mixing as well as disposal costs such as those associated withsaltwater disposal.

Applicant has surprisingly discovered that polymers substituted withamines, alkyls, and/or alkyl amines are effective at reducing orpreventing soil swelling such as of clay and other materials commonlyassociated in mining and drilling operations. Soils includes anymaterials to be excavated or drilled including, but not limited tominerals, dirt, organic material, inorganic material, shale, red mud,rock, mudrock, clay, slag, tailings and combinations thereof. Preferredfunctionalized polymers of the invention include polymers such as, forexample but not limited to polysaccharide, dextran, guar gum, chitosan,scleroglucan, welan, xanthan gum, schizophyllan, levan and cellulose.Preferred functionalized polysaccharides include, for example,polysaccharides substituted or modified with alkyl groups or moietiessuch as, for example, aldehyde, alkane, alkene, alkyne, aryl, and otherhydrocarbon. Examples of substituted polysaccharides of the inventioninclude, polysaccharides substituted with amine (e.g., primary amine),diamine and tetra-amine groups, polysaccharides substituted with alkylgroups or moieties, and/or polysaccharides substituted with alkylaminemoieties. Preferred examples include methyl, ethyl, propyl and isopropylsubstituted polysaccharides and/or oxidized polysaccharides,monoaldehyde, dialdehyde, and/or polyaldehyde substitutedpolysaccharides and/or oxidized polysaccharides, and monoamine, diamine,triamine, and polyamine substituted polysaccharides and/or oxidizedpolysaccharides. Especially preferred examples include dextran (e.g., abranched polyglucan composed of many glucose molecules) in chains ofvarying lengths. Preferably the polymers are from about 2 kD to about100,000 kD, more preferably from about 5 kD to about 50,00,000 kD, morepreferably from about 100 kD to about 10,000 kD, and combinationsthereof. Preferably polymers comprise from 1-3 alkyl/amine substitutionsper polymer unit, preferably a monosaccharide or glucose unit.Substitutions can range from 1 to 100 percent of the monosaccharideunits of the polysaccharide containing substitutions. The degree andamount of substitution and coupled moieties may depend on the particularmoiety or moieties substituted, and may be determined empirically bythose skilled in the art. Preferably units that contain moieties maycomprise from 5 to 80 percent, preferably from 10 to 50 percent,preferably from 30 to 70 percent, or preferably from 10 to 50 percent.Also preferred are polysaccharides containing multiple differentsubstitutions including but not limited to alkyl and amine moietysubstitutions.

Clay Control Additive Handling, Mixing and Field Operation

One embodiment of the invention is directed to functionalized polymersof the invention used to control the swelling of sons such as, forexample, sons containing days. These day-controlling polymers of theinvention are preferably chemically engineered (functionalized andoptionally modified by, for example, oxidation) to encapsulate mineralsfound in day sons and/or colloidal particles common in reservoirs (e.g.,man-made reservoirs, unconventional reservoirs, work-site overflow pits,fluid holding pits, stimulation fluids). The day minerals encounteredare preferably illite (e.g., detrital and diagenetic), smectite, mixedillite and smectite, kaolinite, chlorite, muscovite, biotite, talc,glauconite, sepiolite, saponite and combinations thereof. In addition,the functionalized polymers of the invention encapsulate various formsof colloidal oxides such as, for example, preferably hematite, goethite,ilmenite, colloidal silica, calcite, dolomite and combinations thereof.

Functionalized polymers of the invention are preferably mixed with, forexample, fluids associated with drilling activities as fluidcompositions. The preferred concentration of the functionalized polymeris from about one percent to about 75 percent, or from about 10 percentto about 50 percent, or from about 10 percent to about ninety percent,or from about 25 percent to about 75 percent, or any combinationthereof. Preferred concentrations of the functionalized polymers of theinvention in an associated fluid at a work site is generally within thepreferred ranges and can be tailored to more exact amounts depending onthe particular compound utilized. When desired, concentrations can becalculated based on molecular function and/or determined empirically.Functionalized polymers of the invention are preferably utilized fordrill string curing (e.g., string pickling), well killing, matrixacidizing stimulation, well abandonment, well bore clean-up, open wellbore conditioning, hydraulic fracturing (e.g., primary stimulation ofunconventional shale and limestone reservoirs), inhibitor, chemicalstabilization treatments and similar processes.

Functionalized polymers of the invention preferably function in aqueous(e.g. water-based formulations) (WBF) and hydrocarbon- or oil-basedformulations (OBF) as fluids for example, in dispersed, non-dispersedand polymer based drilling, drill-in and stimulation fluids. The generalstimulation fluids include: 1) “slick” water which comprises a range ofone or more of make-up waters, clay control agents, surfactants andanti-corrosion additives; 2) hybrid systems that include, for example,friction reducers, clay control additives, anti-freezers (e.g., CaCl₂,KCl) surfactants, gel breakers, and anti-corrosion additives; 3) linearand cross linked gel fluids comprised of, for example, guar and xanthangums, surfactants, clay control agents, anti-corrosion agents, viscosityenhancers (cross-linkers), viscosity reducers (breakers), carrier oils(diesel, synthetic olefin oils, and the like), and buffers (acids andbases). Each of these fluids are routinely utilized in the stimulationand drilling industry.

Functional polymers of the invention are preferably provided as aliquid, for example, to a well site either in one cubic meter vessels(referred to as “totes”) or in bulk form (e.g., 1,000-5,000 gallontanks). Hydraulic or electrical pumps transport the liquid to acentralized mixing tank or a fluid stock tank (e.g., as immediate orlong-term storage). Tanks are used for mixing and blending of the fullrange of drilling fluids described herein. The mixing protocol can varyfrom one operation to the next with respect to the order of addition ofthe various agents, compounds and additives. Preferably thefunctionalized polymers of the invention are mixed centrally or inpartial batches for final blending in tanks (e.g., from 500 to 20,000gallons) either in compartments or in whole fluid chambers. Tanks may befabricated to minimize corrosion (e.g., stainless steel, aluminum, PVC)or lined for additional strength and fluid management. Functionalizedpolymers of the invention are preferably mixed with a range of make-upwaters such as, for example, 100 percent fresh water (potable ornon-potable) from local water wells and resources, to blends of producedwater from the well ranging from 1-50 percent produced water with freshwater, to a range of treated produced water as make-up water.

Mixing tanks typically feed high pressure pumps designed to deliver arange of fluid viscosities and densities to the subsurface as desiredfor the particular operation. Fluids are transported with standardpressurized suction lines and pumping units utilized in the industry.Functionalized polymers of the invention as liquids can be utilized withreciprocating pumps, the full range of positive displacement hydraulicpumps, high pressure non-cavitating pumps, and cavitating jet pumps, toname a few. Typical pumping pressures utilized for the particularoperation which can be 1,000 psi or much more, such as for example,1,000 to as much as 10,000 psi or even more, so are not limited to thisrange. These pumping units can be truck-mounted, skid mounted or fixedland-based units at the well site. Functionalized polymers of theinvention containing fluids are then discharged through typicalmonitoring and control units (which are sometimes referred to asChristmas Trees) through pressurized discharge pipes and hoses used inthe industry routinely. Fluids containing functionalized polymers of theinvention are preferably pumped directly downhole (e.g., bullheaded) orcan be pumped through specialized “spot” pumping equipment known ascoiled tubing pressure pumping.

Functionalized polymers of the invention whether as dry compositions oras fluid compositions are straightforward to create and inexpensivelymanufactured in large quantities. Processes for manufacture includecombining, for example, dextran at an acid or alkaline pH, with an aminechloride for a period of time sufficient to allow for completion of thechemical conversion (e.g., generally minutes to hours) at an elevatedtemperature (e.g., generally above ambient temperature and less thanabout 200° C., preferably from about 50-150° C., more preferably about60° C.) and precipitating the substituted polymer with an alcohol.Obtaining a degree or percent of substitutions along the polymer isknown or determined empirically by those skilled in the art. FIGS. 1A-1Ilist a number of functionalized polymers of the invention and providesboth chemical structures 1-9 and common chemical names. Functionalizedpolymers of the invention include functional modifications andderivatives of the listed chemical structures 1-9 including saltsthereof. Modifications and/or derivatives include compounds with more orless chemical moieties, substitution and/or side chains, but areotherwise functional according to the invention. Preferredfunctionalization includes, but is not limited to modification of apolysaccharide and/or a modified polysaccharide molecule (e.g.,oxidized, acid or alkaline pH treated) with one or morediethylaminoethyl (DEAE), diethylethanolamine, diethylamine, ethylamine,ethanol amine, and amine moieties.

Functionalized polymers of the invention are preferably liquids, but maybe manufactured as semi-solids such as gels and pastes, or solids suchas, for example, powders or blocks, which are preferably solubilized ina liquid before use. As these functionalized polymers are preferablywater soluble, the preferred solvent is water and other water-based orpolar substances, but can be non-polar or hydrophobic depending on theparticular compound and/or the presence of additional substances withinthe stabilization composition. Preferably the functionalized polymercompositions of the invention contain no or only small amounts of sodiumand/or other single molecule cations (e.g. less than 1,000 ppm,preferably less than 100 ppm, more preferably less than 10 ppm or morepreferably less than 1 ppm calcium, potassium and/or sodium). Alsopreferably the functionalized polymers and compositions of the inventioncontain no ingredients, components or additional chemicals atconcentrations that are or that could be harmful to the user, to theenvironment and/or to any associated materials or equipment of theoperation or even nearby equipment that is otherwise unrelated to thespecific operation.

Preferably functionalized polymers of the invention are manufactured anddistributed in a concentrated form and diluted before use.Concentrations vary depending upon the particular use to which thestabilization composition is applied and also the particular soilconditions (e.g., percent hydrated or dry). Preferred concentrations ofthe functionalized polymers include, for example, from 5-100 percent,from 10-90 percent, from 20-80 percent and from 30-70 percent when usedwith a solvent. Preferred concentrations for use in drilling andfracking procedures include, for example, from 0.01-10 percent, from 1-9percent, from 2-8 percent and from 3-7 percent.

Additional substances that can be included with the functionalizedpolymer compositions of the invention include, for example,surfactants/defoaming agents, detergents, chelators, and/or buffers.Preferred surfactants/defoaming agents include silicone polymer,polysorbate, antifoam A, Tween, or any combination thereof. Preferreddetergents include sodium dodecyl sulfate, lithium dodecyl sulfate,sodium taurodeoxycholate, sodium taurocholate, sodium glycocholate,sodium deoxycholate, sodium cholate, sodium alkylbenzene sulfonate,N-lauroyl sarcosine, or any combination thereof. Preferred chelatorsinclude ethylene glycol tetra acetic acid,hydroxyethylethylenediaminetriacetic acid, diethylene triamine pentaacetic acid, N,N-bis(carboxymethyl)glycine, ethylenediaminetetraacetic,citrate anhydrous, sodium citrate, calcium citrate, ammonium citrate,ammonium bicitrate, citric acid, diammonium citrate, ferric ammoniumcitrate, lithium citrate, or any combination thereof. Preferred buffersinclude tris(hydroxymethyl) aminomethane, citrate,2-(N-morpholino)ethanesulfonic acid,N,N-Bis(2-hydroxyethyl)-2-aminoethanesulfonic acid,1,3-bis(tris(hydroxymethyl)methyl amino)propane,4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid, 3-(N-morpholino)propanesulfonic acid, bicarbonate, phosphate, or any combinationthereof. The pH of the compositions of the invention may be any pH at orbetween pH 1 and pH 14, and is preferably between about pH 4-9, morepreferably about pH 5-8 and more preferably about pH 7. Concentrationsof preferred additives of the invention are detergents at from about0.001 percent to about 0.1 percent (wt./vol.); chelators at from about0.01 μM to about 1 mM; and buffers at from about 10 μM to about 10 mM.

Also preferably, the functionalized polymers of the invention areeffective over a wide temperature range and do not solidify at lowtemperatures, as compared to ambient. Preferable functionalized polymersand compositions of the invention remain liquid at temperatures at andbelow 10° C., at and below 5° C., at and below 0° C., at and below minus5° C., and at and below minus 10° C. More preferably, the functionalizedpolymers and compositions of the invention are useful over a temperaturerange of minus 10° C. and greater. Higher temperatures are notnecessarily an issue with stabilization, although functionalizedpolymers and compositions of the invention can be used at ambienttemperatures, and temperatures at or greater than 25° C., 30° C., 35°C., 40° C., 45° C., 50° C. and even higher.

Embodiments of the invention may comprise functionalized polymers plusstabilizer and other compositions that include, for example, uniquenucleic acid and/or amino acid sequences, unique chemical codes, uniqueparticles, unique nanoparticles (e.g., single-walled, double-walled andmulti-walled carbon nanotubes), or other identifiable tags can bedetected and identified after use such as, for example, in productsproduced and/or the environment. Detection of unique and identifiabletags allow for tracking and monitoring of present and prior use of thefunctionalized polymers and compositions of the invention. Monitoringand tracking can be used for environmental purposes, agriculturalpurposes, assessing disbursement including patterns of disbursement andtiming of degradation, and other purposes.

Another embodiment of the invention is directed to methods ofstabilizing soils. Functionalized polymers (e.g. polymer compoundsthemselves) and/or compositions of the invention are contacted withsoils before, during or after mining, drilling or another excavationprocedure. By contacting inventive functionalized polymers and/orcompositions before or during excavation, excavation can proceedsmoothly and quickly without the need to periodically stop excavationfor stabilization control. Continuous stabilization occurssimultaneously with excavation. Alternatively, and for example indrilling and fracking procedures, the ground is drilled and immediatelythereafter, a fluid including the stabilizing functionalized polymersand/or compositions of the invention flushed into the drilled spaces.Alternatively, stabilization can be used periodically during excavationto stabilize a region of soil in advance of, during and/or soon afterexcavation, thus allowing excavation to proceed smoothly and created astable space. Contact may comprise mixing the functionalized polymersand/or compositions of the invention with soil of the excavation areaand/or other materials forming a thixotropic fluid. A preferred methodcomprises mixing the compounds and/or compositions of the invention witha drilling fluid, such as for example, pumping fluids, drilling mud,xanthan gum, and the like, and flushing the drilled space with themixture. Preferably, 10 parts drilling fluid is mixed with one-partstabilizing functionalized polymers and/or compositions of theinvention. The exact proportions may vary depending on the drillingfluid and stabilizing functionalized polymers chosen and can beempirically determined by one skilled in the art. Ratios of drillingfluid to functionalized polymer include the proportions 100:1, 50:1,20:1, 10:1, 5:1, 2:1, 1:2, 1:5, 1:10, 1:20, 1:50, and 1:100, includingthose ratios in between these ranges. The resulting fluid can have aconsistency from molasses to a paste such as, for example, a viscosityof from about 50-10,000 cP, preferably from about 100-500 cP, and morepreferable from about 200-300 cP. Alternatively, functionalized polymersand/or compositions of the invention can be deposited directly ontosoils such as an excavation site, in concentrated or diluted forms.

Another embodiment of the invention is directed to methods ofstabilizing by-products of mining and excavations. Preferably, theby-products are soils that contain clay and other water-absorbingcomposition. Contact of the functionalized polymers and/or compositionsof the invention with the by-products stabilizes the by-products,specifically preventing swelling. Stabilization prevents expansion ofthe by-products outside of a containment area and, for example, canprevent catastrophic break-down of containment.

Preferably, the stabilizer is a single fluid of the invention which canbe used alone or in combination with other wellbore fluids and remainseffective over broad range of pH values and temperatures.

The following examples illustrate embodiments of the invention, butshould not be viewed as limiting the scope of the invention.

EXAMPLES Example 1 HTMAC Dextran from Epoxide HP4596

HTMAC (hydroxypropyltrimethyl ammonium chloride) dextran directly fromepoxide was obtained by reacting dextran with glycidyltrimethyl ammoniumchloride in the presence of caustic and water at elevated temperatures(preferable from 50-100° C.).

Example 2 HTMAC Dextran from Hydroxy Chloride HP4019

First step in the synthesis of HTMAC (hydroxypropyltrimethyl ammoniumchloride) dextran was obtained by obtaining epoxide from(3-Chloro-2-hydroxypropyl)trimethyl ammonium chloride in the presence ofcaustic and water at elevated temperatures (preferable from 50-100° C.).Formed epoxide (in situ) and dextran was reacted with caustic in waterat elevated temperatures (preferable from 50-100° C.) yielded HTMACDextran.

Example 3 Amino Dextran (Partially Oxidized Sugar Dextran Diethyl Amine)HP3650

Amino dextran was obtained by reacting dextran with sodium periodate inwater at room temperature (preferable from about 20-22° C.) followed byethylene diamine addition in water at room temperature and final stepfollowed by reduction of formed imine with sodium borohydride in waterat room temperature.

Example 4 Diethylethanolamine Dextran HP7577

Diethylethanolamine dextran was obtained by reacting dextran with2-chloro-N,N-diethylamine in the presence of caustic and water atelevated temperatures (preferable from 50-100° C.).

Example 5 Ethylamine Dextran HP3670

Ethylamine dextran was obtained by reacting dextran with2-chloroethylamine in the presence of caustic and water at elevatedtemperatures (preferable from 50-100° C.).

Example 6 Amino Levan (Partially Oxidized Sugar Levan Diethyl Amine)HP3816

Amino levan was obtained by reacting levan with sodium periodate inwater at room temperature followed by ethylene diamine addition in waterat room temperature and final step followed by reduction of formed iminewith sodium borohydride in water at room temperature.

Example 7 Amino Guar (Partially Oxidized Sugar Guar Diethyl Amine)HP3945

Amino guar was obtained by reacting guar with sodium periodate in waterat room temperature followed by ethylene diamine addition in water atroom temperature and final step followed by reduction of formed iminewith sodium borohydride in water at room temperature.

Example 8 Capillary Suction Time (CST) Test

HP4019, HP7577, HP3650, HP4596, HP3670 and HP3816 solution claystabilizer performance were evaluated by capillary suction time tests(OFITE capillary suction timer). All the solutions were prepared bydissolving appropriate amount of polysaccharide derivatives in tapwater. The performances of these products were compared to theperformance of standards (choline chloride, calcium chloride). HP4019,HP7577, HP3650, HP4596, HP3670, HP3816 and dextran solutions wereprepared at various concentrations. The test fluids are prepared fromeach solution of HP4019, HP7577, HP3650, HP4596, HP3670 and HP3816 at 1gpt (gallons per thousand) and 2 gpt concentrations. 1 g shale was addedin 15 mL of each test fluid and test fluids were mixed for 10 to 15minutes. CST ratios are calculated by dividing compound CST values withblank (distilled water) CST values and results are shown in Table 1.Smaller CST ratios indicate better performance of the clay stabilizationproducts. HP3816, HP3650, HP4596 and HP3670 showed superior performancein comparison to the commercial choline chloride and calcium chlorideproducts. Moreover pure un-functionalized dextran gave very high CSTratio indicates that amine functionalization is key for the claystabilization

TABLE 1 Capillary suction time test results at 1 gpt and 2 gpt CholineConcentration chloride CaCl₂ Dextran of Solids HP4596 HP3650 HP3670HP4019 HP7577 HP3816 70% 15% 10% 1 gpt 0.068 0.072 0.077 0.13 0.17 0.0660.12 0.39 2.39 2 gpt 0.092 0.067 0.067 0.13 0.13 0.064 0.11 0.26 3.34

Other embodiments and uses of the invention will be apparent to thoseskilled in the art from consideration of the specification and practiceof the invention disclosed herein. All references cited herein,including all publications, and all U.S. and foreign patents and patentapplications are specifically and entirely incorporated by reference.The term comprising, where ever used, is intended to include the termsconsisting and consisting essentially of. Furthermore, the termscomprising, including, and containing are not intended to be limiting.It is intended that the specification and examples be consideredexemplary only with the true scope and spirit of the invention indicatedby the following claims.

What is claimed is the following:
 1. A process comprising: providing acomposition comprising an aqueous liquid and a partially oxidizedpolysaccharide in which glycosidic bonds are retained from a parentpolysaccharide and partial oxidation comprises oxidative opening of amonosaccharide unit of the parent polysaccharide; wherein the partiallyoxidized polysaccharide comprises an amine moiety at a site of oxidativeopening; and introducing the composition into a clay-containingformation; wherein the partially oxidized polysaccharide stabilizes aclay in the clay-containing formation.
 2. The process of claim 1,wherein the composition is introduced into the clay-containing formationduring a drilling operation.
 3. The process of claim 1, wherein thecomposition is introduced into the clay-containing formation during astimulation operation.
 4. The process of claim 3, wherein thestimulation operation is a matrix acidizing operation or a hydraulicfracturing operation.
 5. The process of claim 1, wherein the compositionis introduced into the clay-containing formation during a clean-upoperation.
 6. The process of claim 1, wherein the partially oxidizedpolysaccharide comprises a partially oxidized dextran, a partiallyoxidized levan, or a partially oxidized guar.
 7. The process of claim 1,wherein the parent polysaccharide comprises a plurality ofmonosaccharide units and about 5%-80% of the plurality of monosaccharideunits are oxidatively opened and bear an amine moiety at the site ofoxidative opening.
 8. The process of claim 1, wherein the compositionfurther comprises a surfactant, a defoaming agent, a detergent, achelator, a buffer, an anti-corrosion additive, an anti-freezer, a gelbreaker, an anti-corrosion additive, a breaker, a crosslinker, a gellingagent, a carrier oil, or any combination thereof.
 9. The process ofclaim 1, wherein the partially oxidized polysaccharide prevents swellingof the clay.
 10. The process of claim 1, wherein the amine is analkylamine.
 11. The process of claim 10, wherein the alkylamine is adiamine, a first amine group of the diamine being covalently bonded tothe site of oxidative opening and a second amine group of the diaminebeing tethered via an alkyl group to the site of oxidative opening. 12.A composition comprising: a partially oxidized polysaccharide in whichglycosidic bonds are retained from a parent polysaccharide and partialoxidation comprises oxidative opening of a monosaccharide unit of theparent polysaccharide; wherein the partially oxidized polysaccharidecomprises a partially oxidized dextran, a partially oxidized levan, or apartially oxidized guar, wherein the partially oxidized polysaccharidecomprises an amine moiety at a site of oxidative opening, and whereinthe partially oxidized polysaccharide promotes stabilization of a clayin a clay-containing formation.
 13. The composition of claim 12, furthercomprising: an aqueous liquid.
 14. The composition of claim 12, furthercomprising: a surfactant, a defoaming agent, a detergent, a chelator, abuffer, an anti-corrosion additive, an anti-freezer, a gel breaker, ananti-corrosion additive, a breaker, a crosslinker, a gelling agent, acarrier oil, or any combination thereof.
 15. The composition of claim12, wherein the parent polysaccharide comprises a plurality ofmonosaccharide units and about 5%-80% of the plurality of monosaccharideunits are oxidatively opened and bear an amine moiety at the site ofoxidative opening.
 16. The composition of claim 12, wherein the amine isan alkylamine.
 17. The composition of claim 16, wherein the alkylamineis a diamine, a first amine group of the diamine being covalently bondedto the site of oxidative opening and a second amine group of the diaminebeing tethered via an alkyl group to the site of oxidative opening.